Cationic-stabilized dispersions, hybridized cationic-stabilized dispersions, in-mold coated articles prepared utilizing such stabilized dispersions, and methods for manufacturing same

ABSTRACT

A cationic-stabilized dispersion for use in fabricating an in-mold coated article including at least one of a cationic-stabilized polyurethane dispersion, a cationic-stabilized acrylic dispersion, a cationic-stabilized polyacrylamide dispersion, a cationic-stabilized polyallylamine dispersion, a cationic-stabilized polyetheramine dispersion, and a cationic-stabilized chitosan dispersion.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.16/290,069, entitled “CATIONIC-STABILIZED DISPERSIONS, HYBRIDIZEDCATIONIC-STABILIZED DISPERSIONS, IN-MOLD COATED ARTICLES PREPAREDUTILIZING SUCH STABILIZED DISPERSIONS, AND METHODS FOR MANUFACTURINGSAME,” filed Mar. 1, 2019, which is a continuation of U.S. applicationSer. No. 15/644,742, entitled “CATIONIC-STABILIZED DISPERSIONS,HYBRIDIZED CATIONIC-STABILIZED DISPERSIONS, IN-MOLD COATED ARTICLESPREPARED UTILIZING SUCH STABILIZED DISPERSIONS, AND METHODS FORMANUFACTURING SAME,” filed Jul. 8, 2017, now U.S. Pat. No. 10,227,503,which is a continuation of U.S. application Ser. No. 14/833,416,entitled “CATIONIC-STABILIZED DISPERSIONS, HYBRIDIZEDCATIONIC-STABILIZED DISPERSIONS, IN-MOLD COATED ARTICLES PREPAREDUTILIZING SUCH STABILIZED DISPERSIONS, AND METHODS FOR MANUFACTURINGSAME,” filed Aug. 24, 2015, now U.S. Pat. No. 9,738,812—which are herebyincorporated herein by reference in their entirety, including allreferences cited therein.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates in general to cationic-stabilizeddispersions, such as, for example, cationic-stabilized polyurethanedispersions, cationic-stabilized acrylic dispersions,cationic-stabilized polyacrylamide dispersions, cationic-stabilizedpolyallylamine dispersions, cationic-stabilized polyetheraminedispersions, and cationic-stabilized chitosan dispersions. The presentinvention further relates to cationic-stabilized dispersions hybridizedwith nonionic compounds, including non-polymeric, oligomeric, andpolymeric resins—just to name a few. In addition, the present inventionrelates to in-mold coated articles prepared utilizing suchcationic-stabilized dispersions optionally hybridized with nonioniccompounds. Such in-mold coated articles are suitable for use in, forexample, residential, commercial, industrial, and/or military productsin any one of a number of industries, including, but not limited to,aerospace, automotive, construction, furniture, health care, and/ormarine industries—just to name a few.

2. Background Art

Cationic dispersions have been known in the field of chemistry foryears. See, for example, U.S. Pat. No. 6,339,125 entitled “CationicPolyurethane Dispersion and Composition Containing Same,” U.S. Pat. No.6,017,998 entitled “Stable Aqueous Polyurethane Dispersions,” U.S. Pat.No. 5,807,919 entitled “Water-Based Sulfonated Polymer Compositions,”U.S. Pat. No. 5,723,518 entitled “Aqueous Two-Component PolyurethaneCoating Compositions and a Method for Their Preparation,” U.S. Pat. No.5,700,867 entitled “Aqueous Dispersion of an AqueousHydrazine-Terminated Polyurethane,” U.S. Pat. No. 5,696,291 entitled“Cationic Polyurethane Compositions, Quaternary Ammonium Salts andMethods for Their Preparation,” U.S. Pat. No. 5,523,344 entitled“Water-Based Adhesive Formulation Having Enhanced Characteristics,” U.S.Pat. No. 5,043,381 entitled “Aqueous Dispersions of a Nonionic, WaterDispersible Polyurethane Having Pendent Polyoxyethylene Chains,” U.S.Pat. No. 7,964,665 entitled “Cationic Polyurethane Resin AqueousDispersion, Ink-Jet Recording Medium Using The Same,” U.S. PatentApplication Publication No. 2009/0105411 A1 entitled “Aqueous Non-IonicHydrophilic Polyurethane Dispersions, and a Continuous Process of Makingthe Same,” and U.S. Patent Application Publication No. 2005/0182187 A1entitled “Polyurethane Dispersions and Coatings Made Therefrom”—all ofwhich are hereby incorporated herein by reference in theirentirety—including all references cited therein.

Furthermore, in-mold coated articles have been known in the art forseveral years. See, for example, U.S. Pat. No. 6,656,596 entitled“Decorative Automotive Interior Trim Articles with Cast Integral LightStable Covering and Process for Making the Same,” U.S. Pat. No.5,906,788 entitled “Dual Cure, In-Mold Process for ManufacturingAbrasion Resistant, Coated Thermoplastic Articles,” U.S. Pat. No.5,662,996 entitled “Method for Manufacturing Self-Supporting SyntheticTrim Parts and Thus Manufactured Trim Parts,” U.S. Pat. No. 5,418,032entitled “Vehicle Interior Door Panel,” U.S. Pat. No. 5,411,688 entitled“Method for Forming Plastic Molded Panels with Inserts,” U.S. Pat. No.5,242,738 entitled “Surface Layer of Interior Article,” U.S. Pat. No.4,902,578 entitled “Radiation-Curable Coating for ThermoplasticSubstrates,” U.S. Pat. No. 4,830,803 entitled “Method of Making a MoldedArticle of Methacrylic Resin,” U.S. Pat. No. 3,248,467 entitled “MoldingProcess,” U.S. Patent Application Publication No. 2003/0104168 A1entitled “In-Mold-Coated Automotive Interior and Other Products, andMethods for Manufacturing Same,” European Patent Application No.1,079,962 B1 entitled “Decorative Automotive Interior Trim Articles withIntegral In-Mold Coated Polyurethane Aromatic Elastomer Covering andProcess for Making the Same,” and International Publication No. WO99/61216 entitled “Decorative Automotive Interior Trim Articles withIntegral In-Mold Coated Polyurethane Aromatic Elastomer Covering andProcess for Making the Same,” all of which are hereby incorporatedherein by reference in their entirety—including all references citedtherein.

While the utilization of in-mold coated articles has become increasinglypopular in several industries, to the best of Applicant's knowledge,cationic-stabilized dispersions optionally hybridized with nonioniccompounds and certain embodiments thereof, have not been used to providesoft feeling and robust in-mold coated articles that process well.Indeed, historically the field of in-mold coatings for polyurethanesubstrates, and other substrates, has been dominated by waterbornecoatings that are anionically (containing carboxyl functionalityneutralized with an amine and stable at basic pH or non-ionically(pH-independent hydrophilic groups in the backbone) stabilized.

It is therefore an object of the present invention, among other objects,to provide novel, soft feeling and robust in-mold coated articles thatare prepared utilizing cationic-stabilized dispersions and hybridizedvariants thereof. It is also an object of the present invention toprovide methods for manufacturing such novel in-mold articles in arepeatable manner.

These and other features, advantages, and objects of the presentinvention will be further understood and appreciated by those skilled inthe art by reference to the following specification, claims, chemicalstructures, and any appended drawings.

SUMMARY OF THE INVENTION

The present invention is directed to a cationic-stabilized dispersionfor use in fabricating an in-mold coated article comprising: one or moreof a cationic-stabilized polyurethane dispersion, a cationic-stabilizedacrylic dispersion, a cationic-stabilized polyacrylamide dispersion, acationic-stabilized polyallylamine dispersion, a cationic-stabilizedpolyetheramine dispersion, and a cationic-stabilized chitosandispersion.

In a preferred embodiment of the present invention, thecationic-stabilized dispersion preferably comprises acationic-stabilized polyurethane dispersion. In this embodiment, thecationic-stabilized polyurethane dispersion preferably comprises analiphatic polyurethane dispersion and/or a cationic-stabilizedpolyurethane dispersion that is void of free isocyanate.

In another preferred embodiment of the present invention, thecationic-stabilized polyurethane dispersion comprises a cationicpolyurethane resin aqueous dispersion, wherein a cationic polyurethaneresin including a structural unit represented by structure (I) isdispersed in an aqueous medium, and the content of a cationic aminogroup of the structural unit in the cationic polyurethane resin isapproximately 0.005 to approximately 1.5 equivalents/kg:

wherein R₁ comprises an alkylene group which may include an alicyclicstructure, a residue of bivalent phenol, or a polyoxyalkylene group,wherein R₂ and R₃ each independently comprise an alkyl group which mayinclude an alicyclic structure, and R₄ comprises a hydrogen atom or aresidue of a quaternizing agent which is introduced by a quaternizingreaction and X⁻ represents an anionic counter ion.

In yet another preferred embodiment of the present invention, thecationic-stabilized dispersion comprises a cationic-stabilizedpolyurethane dispersion having approximately 10 to approximately 60percent solids, a Tg of approximately −40 degrees centigrade toapproximately 20 degrees centigrade, and volatile organic content ofless than approximately 10 parts per million.

In another aspect of the present invention, the cationic-stabilizeddispersion comprises a cationic-stabilized polymeric acrylic dispersion.Preferably, the cationic-stabilized polymeric acrylic dispersioncomprises a hydroxyl functional cationic acrylic copolymer thatcrosslinks with polyisocyanates and epoxy silanes at ambienttemperatures.

In a preferred embodiment of the present invention, thecationic-stabilized polymeric acrylic dispersion comprises at least oneof an ethylene acrylic acid copolymer and a styrene-acrylic copolymer.

In another preferred embodiment of the present invention, thecationic-stabilized dispersion comprises a cationic-stabilized polymericacrylic dispersion having approximately 10 to approximately 60 percentsolids, a Tg of approximately 15 degrees centigrade to approximately 50degrees centigrade, and a viscosity ranging from approximately 200centipoise to approximately 800 centipoise at 25 degrees centigrade.

In yet another aspect of the present invention, the cationic-stabilizeddispersion preferably comprises a cationic-stabilized polyetheraminedispersion.

In a preferred embodiment of the present invention, thecationic-stabilized dispersion comprises one or more of a tri-functionalprimary amine, a di-functional primary amine, and/or a di-functionalsecondary amine.

In one embodiment of the present invention, the cationic-stabilizedpolyetheramine dispersion comprises the structure of formula II:

wherein R₁-R₆ are each independently selected from the group consistingof H, an amine, an ammonium constituent, and an alkyl, cycloalkyl,polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy,alkanoyl, aroyl, and/or alkyl-alkenyl group containing approximately 1to approximately 25 carbon atom(s), with the proviso that at least threeof R₁-R₆ consist of an amine or an ammonium constituent and at least oneof R₁-R₆ consists of an ammonium constituent under acidic conditions,and wherein the sum of x, y, and z ranges from approximately 50 toapproximately 90.

In another embodiment of the present invention, the cationic-stabilizedpolyetheramine dispersion comprises the structure of formula III:

wherein R₁-R₄ are each independently selected from the group consistingof H, an amine, an ammonium constituent, and an alkyl, cycloalkyl,polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy,alkanoyl, aroyl, and/or alkyl-alkenyl group containing approximately 1to approximately 25 carbon atom(s), with the proviso that at least twoof R₁-R₄ consist of an amine or an ammonium constituent and at least oneof R₁-R₄ consists of an ammonium constituent under acidic conditions,and wherein x ranges from approximately 5 to approximately 70.

In a preferred embodiment of the present invention, thecationic-stabilized polyetheramine dispersion comprises a total amineconcentration of approximately 0.40 meq/g to approximately 0.98 meq/g.

In another aspect of the present invention, the cationic-stabilizeddispersion comprises a cationic-stabilized polyacrylamide dispersion, acationic-stabilized polyallylamine dispersion and/or acationic-stabilized chitosan dispersion.

The present invention is also directed to a hybridizedcationic-stabilized dispersion for use in fabricating an in-mold coatedarticle comprising: one or more of a cationic-stabilized polyurethanedispersion, a cationic-stabilized acrylic dispersion, acationic-stabilized polyacrylamide dispersion, a cationic-stabilizedpolyallylamine dispersion, a cationic-stabilized polyetheraminedispersion, and a cationic-stabilized chitosan dispersion, wherein thecationic-stabilized dispersion is hybridized with at least one ofnonionic, oligomeric resins and nonionic, polymeric resins.

The present invention is further directed to an in-mold coated articlecomprising: an inner surface and an outer surface, characterized in thatthe in-mold coated article is prepared in association with acationic-stabilized dispersion. In this embodiment, thecationic-stabilized dispersion comprises one or more of acationic-stabilized polyurethane dispersion, a cationic-stabilizedacrylic dispersion, a cationic-stabilized polyacrylamide dispersion, acationic-stabilized polyallylamine dispersion, a cationic-stabilizedpolyetheramine dispersion, and/or a cationic-stabilized chitosandispersion.

The present invention is also directed to a method for manufacturing anin-mold coated article comprising the steps of: (a) optionally applyinga mold release agent to at least a portion of a tool surface; (b)applying a cationic-stabilized dispersion to at least a portion of thetool surface and/or the mold release agent; and (c) associating asubstrate with the tool surface having the optional mold release agentand the cationic-stabilized dispersion to, in turn, generate an in-moldcoated article.

DETAILED DESCRIPTION OF THE INVENTION

While this invention is susceptible of embodiment in many differentforms, there is described herein in detail several specific embodimentswith the understanding that the present disclosure is to be consideredas an exemplification of the principles of the invention and is notintended to limit the invention to the embodiments illustrated.

In accordance with the present invention, in-mold coated articles aredisclosed herein which are prepared utilizing cationic-stabilizeddispersions and cationic-stabilized dispersions hybridized with nonioniccompounds. The articles are preferably fabricated from, for example,polyurethane (e.g., sprayskin, foam, RIM, slush TPU), vinyl (e.g., slushvinyl), thermoplastic polyolefins, elastomers, among others.

In further accordance with the present invention, thecationic-stabilized dispersions preferably comprise cationic-stabilizedpolyurethane dispersions, cationic-stabilized acrylic dispersions,cationic-stabilized polyacrylamide dispersions, cationic-stabilizedpolyallylamine dispersions, cationic-stabilized polyetheraminedispersions, and/or cationic-stabilized chitosan dispersions. Thedispersions of the present invention may be hybridized with nonioniccompounds, including, for example, non-polymeric, oligomeric, andpolymeric resins.

The novel dispersion coatings disclosed herein are characterized by thecationic nature of the aqueous or waterborne resin(s) being used. In oneembodiment, the cationic resins are characterized by amine functionalityon the backbone and, as such, are stable aqueous dispersions atgenerally alkaline or basic pHs. The amine functionality on the backboneof these resins affords excellent adhesion to, for example, apolyurethane article which is placed in the mold following the coatingapplication. Such improved adhesion provides the ability to process overa wide range of substrates at varying NCO/OH ratios. Further benefitsare extremely fast dry times, near zero-VOC emission, as well as theability to be cross-linked at the amine sites for improved physicalproperties.

Without being bound by any one particular theory, it is believed that,in one embodiment, when the dispersion coating is sprayed into the mold,one or more amine functional groups or moieties become available as anacid (typically glacial acetic acid or formic acid). Such amine groupsinteract in a plurality of ways with the substrate (e.g., polyurethane)which is subsequently applied to the mold. In the case of primary andsecondary amine functionality, active hydrogens available on the coatingbackbone are believed to allow for a thermodynamically favored reactionsite with the isocyanate portion of the polyurethane material placed inthe mold after the coating. The controlled, yet rapid formation ofcovalent bonds due to amine-isocyanate reactions is believed to providefor enhanced adhesion and exemplary processing. In the case of tertiaryamines and quaternary ammonium salts, the amines may associatethemselves with the polyurethane applied to the mold in the form ofaccelerators for the isocyanate-polyol reaction of the polyurethanesubstrate.

Notwithstanding the foregoing and regardless of the precise mechanism,one unexpected advantage of the cationic nature of thedispersion/coating is a more robust in-mold product which is capable ofbeing applied over a wider range of polyurethane substrates utilizingvarying NCO/OH ratios and catalyst packages. An additional advantage ofthe cationic system is the potential availability of free hydrogens viaamine groups (once the acid evaporates after application) for reactionwith crosslinkers, including epoxy-functional silanes, polyisocyanates,water-reducible epoxy prepolymers, etcetera. One benefit of the addedcrosslinker is to readily modify (e.g., increase or decrease) anyparticular desirable property (e.g., chemical resistance, abrasionresistance, water resistance, toughness, etcetera).

In a first embodiment of the present invention, the cationic-stabilizeddispersion preferably comprises one or more cationic-stabilizedpolymeric acrylic dispersions. Suitable examples include Ottopol K-12,Ottopol K-21-30, Ottopol K-362, Ottopol K-633, Ottopol K-23, OttopolK-65, Ottopol K-66, and Ottopol KX-99 which are commercially availablefrom Gellner Industrial, LLC, Michem Emulsion 09625 which iscommercially available from Michelman, Syntran 6301, Syntran 6302, andSyntran FX30-20 which are commercially available from InterpolymerCorporation, Picassian AC-146 which is commercially available from StahlUSA, and Acrit UW-550CS which is commercially available from TaiseiChemical Industries, Ltd.

In accordance with the present invention, the cationic-stabilizedacrylic dispersions preferably comprise a hydroxyl functional cationicacrylic copolymer that crosslinks with polyisocyanates and epoxy silanesat ambient temperatures. Additionally, the cationic-stabilized acrylicdispersions may also comprise cationic acrylic copolymers, such as anethylene acrylic acid copolymer and/or a styrene-acrylic copolymer.

In one embodiment of the present invention, the cationic-stabilizedpolymeric acrylic dispersions themselves preferably compriseapproximately 10 to approximately 60 percent solids, and more preferablycomprise approximately 20 to approximately 50 percent solids, and yetmore preferably comprise approximately 25 to approximately 45 percentsolids.

Additionally, the cationic-stabilized polymeric acrylic dispersions ofthe present invention preferably comprise a Tg of approximately 0degrees centigrade to approximately 90 degrees centigrade, and morepreferably comprise a Tg of approximately 15 degrees centigrade toapproximately 50 degrees centigrade, and yet more preferably comprise aTg of approximately 20 degrees centigrade to approximately 45 degreescentigrade.

Preferably, the viscosity of the cationic-stabilized polymeric acrylicdispersions themselves range from approximately 50 centipoise toapproximately 5,000 centipoise at 25 degrees centigrade, and morepreferably range from approximately 100 centipoise to approximately2,000 centipoise at 25 degrees centigrade, and yet more preferably rangefrom approximately 200 centipoise to approximately 800 centipoise at 25degrees centigrade.

In one embodiment of the present invention, the concentration of thecationic-stabilized polymeric acrylic dispersion in a net or overallformulation preferably ranges from approximately 20 percent by weight toapproximately 95 percent by weight, and more preferably ranges fromapproximately 40 percent by weight to approximately 90 percent byweight, and yet more preferably ranges from approximately 50 percent byweight to approximately 85 percent by weight.

While specific cationic-stabilized polymeric acrylic dispersions havebeen disclosed, for illustrative purposes only, it will be understoodthat numerous other cationic-stabilized polymeric acrylic dispersionsare likewise contemplated for use—so long as they operate effectively intheir conditions of intended use.

In a second embodiment of the present invention, the cationic-stabilizeddispersions preferably comprise one or more cationic-stabilizedpolyurethane dispersions. Suitable examples include Hydran CP-7010,Hydran CP-7040, and Hydran CP-7050 which are commercially available fromDIC Corporation, Picassian PU-685 which is commercially available fromStahl USA, Superflex 620 and Superflex 650 which are commerciallyavailable from DAI-ICHI KOGYO SEIYAKU Co. Ltd., and Witcobond 213 andWitcobond 781 which are commercially available from ChemturaCorporation.

In one embodiment of the present invention, the cationic-stabilizedpolyurethane dispersions preferably comprise aliphatic polyurethanedispersions and/or polyurethane dispersions that are void of oressentially void of free isocyanate.

In accordance with the present invention, the cationic-stabilizedpolyurethane dispersions preferably comprise a cationic polyurethaneresin aqueous dispersion wherein a cationic polyurethane resin includinga structural unit represented by structure (I) is dispersed in anaqueous medium, and the content of a cationic amino group of thestructural unit in the cationic polyurethane resin is preferably 0.005to 1.5 equivalents/kg, and more preferably 0.01 to 1.0 equivalents/kg,and yet more preferably 0.02 to 0.5 equivalents/kg:

wherein R₁ comprises an alkylene group which may include an alicyclicstructure, a residue of bivalent phenol, or polyoxyalkylene group,wherein R₂ and R₃ each independently comprise an alkyl group which mayinclude an alicyclic structure, and R₄ comprises a hydrogen atom or aresidue of the quaternizing agent which is introduced by thequaternizing reaction and X⁻ comprises an anionic counter ion. Synthesesfor these cationic-stabilized polyurethane dispersions are provided inPCT Pub. No. PCT/JP2005/011736 and its related applications.

In a preferred embodiment of the present invention thecationic-stabilized polyurethane dispersions themselves compriseapproximately 10 to approximately 60 percent solids, and more preferablycomprise approximately 20 to approximately 50 percent solids, and yetmore preferably comprise approximately 25 to approximately 45 percentsolids.

Additionally, the cationic-stabilized polyurethane dispersions of thepresent invention preferably comprise a Tg of approximately −60 degreescentigrade to approximately 90 degrees centigrade, and more preferablycomprise a Tg of approximately −40 degrees centigrade to approximately20 degrees centigrade, and yet more preferably comprise a Tg ofapproximately −40 degrees centigrade to approximately 0 degreescentigrade.

In another embodiment of the present invention, the volatile organiccontent of the cationic-stabilized polyurethane dispersions themselvesis less than approximately 20 parts per million, and more preferablyless than approximately 10 parts per million, and yet more preferablyless than approximately 7.5 parts per million.

Preferably, the concentration of the cationic-stabilized polyurethanedispersion in a net or overall formulation ranges from approximately 20percent by weight to approximately 98 percent by weight, and morepreferably ranges from approximately 60 percent by weight toapproximately 95 percent by weight, and yet more preferably ranges fromapproximately 75 percent by weight to approximately 93 percent byweight.

While specific cationic-stabilized polyurethane dispersions have beendisclosed, for illustrative purposes only, it will be understood thatnumerous other cationic-stabilized polyurethane dispersions are likewisecontemplated for use—so long as they operate effectively in theirconditions of intended use.

In a third embodiment of the present invention, the cationic-stabilizeddispersions preferably comprise one or more cationic-stabilizedpolyetheramine dispersions. Suitable examples include Jeffamine T400,Jeffamine SD-2001, Jeffamine D-2000, Jeffamine T-3000, Jeffamine D-4000,and Jeffamine T-5000 which are commercially available from HuntsmanCorporation, Baxxodur EC 311 and Baxxodur EC 303 which are commerciallyavailable from BASF, and Poly A27-2000 and Poly A37-5000 which arecommercially available from Arch Chemical Inc.

In accordance with the present invention, the cationic-stabilizedpolyetheramine dispersions preferably comprise multi-functional primary,secondary, and tertiary, amines, including, but not limited to,tri-functional primary amines, di-functional primary amines,di-functional secondary amines—just to name a few.

The present invention is also directed to cationic-stabilizedpolyetheramine dispersions which comprise the structure of formula II:

wherein R₁-R₆ are each independently selected from the group consistingof H, an amine, an ammonium constituent, and an alkyl, cycloalkyl,polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy,alkanoyl, aroyl, and/or alkyl-alkenyl group containing approximately 1to approximately 25 carbon atom(s), with the proviso that at least threeof R₁-R₆ consist of an amine or an ammonium constituent and at least oneof R₁-R₆ consists of an ammonium constituent under acidic conditions,and wherein the sum of x, y, and z ranges from approximately 50 toapproximately 90.

In a preferred embodiment of the present invention, R₁, R₃, and R₆comprise an amine or ammonium constituent and R₂, R₄, and R₅ comprise amethyl group, and wherein the sum of x, y, and z comprises approximately85.

The present invention is further directed to cationic-stabilizedpolyetheramine dispersions which comprise the structure of formula III:

wherein R₁-R₄ are each independently selected from the group consistingof H, an amine, an ammonium constituent, and an alkyl, cycloalkyl,polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy,alkanoyl, aroyl, and/or alkyl-alkenyl group containing approximately 1to approximately 25 carbon atom(s), with the proviso that at least twoof R₁-R₄ consist of an amine or an ammonium constituent and at least oneof R₁-R₄ consists of an ammonium constituent under acidic conditions,and wherein x ranges from approximately 5 to approximately 70.

In a preferred embodiment of the present invention, R₁ and R₄ comprisean amine or ammonium constituent and R₂ and R₃ each comprise a methylgroup, and wherein x comprises approximately 6.1 or approximately 68.

It will be understood that the compounds identified supra in structuresII and III are available from Huntsman with amine functionality that canbe altered via pH modifiers—among others.

In another aspect of the present invention, the cationic-stabilizedpolyetheramine dispersions comprise a total amine concentration ofapproximately 0.40 meq/g to approximately 0.98 meq/g, and morepreferably comprise a total amine concentration of approximately 0.44meq/g to approximately 0.90 meq/g, and yet more preferably comprise atotal amine concentration of approximately 0.50 meq/g to approximately0.54 meq/g.

Preferably, the concentration of the cationic-stabilized polyetheraminedispersion in a net or overall formulation ranges from approximately 10percent by weight to approximately 75 percent by weight, and morepreferably ranges from approximately 12 percent by weight toapproximately 50 percent by weight, and yet more preferably ranges fromapproximately 15 percent by weight to approximately 30 percent byweight.

While specific cationic-stabilized polyetheramine dispersions have beendisclosed, for illustrative purposes only, it will be understood thatnumerous other cationic-stabilized polyetheramine dispersions arelikewise contemplated for use—so long as they operate effectively intheir conditions of intended use.

In another embodiment of the present invention, cationic-stabilizeddispersions preferably comprise cationic-stabilized polyacrylamidedispersions (see, for example, Lui, Juan et al., “Aqueous DispersionPolymerization of Acrylamide in Ammonium Chloride Solution withWater-soluble Chitosan as a Stabilizer.” Iranian Polymer Journal 20(11), 2011, 887-896. Print) and/or cationic-stabilized polyallylaminedispersions (see, for example, Jaejung, Park et al., “AggregationProcesses of a Weak Polyelectrolyte, Poly(allylamine) Hydrochloride.”Bull. Korean Chem. Soc. 2008, Vol. 29, No. 1. Print), andcationic-stabilized chitosan dispersions (see European PatentPublication No. 2 221 044 A1). The three above-identified references arehereby incorporated herein by reference in their entirety—including allreferences cited therein.

As will be shown in greater detail in the examples infra, the presentinvention is further directed to cationic-stabilized dispersionshybridized with nonionic compounds, including non-polymeric, oligomeric,and polymeric resins—just to name a few. Preferred, nonionic compoundsinclude, for example, nonionic polyester diols, such as Kuraray P-1010which is commercially available from Kuraray Co., Ltd., polyethyleneglycols, such as Carbowax 200 and Carbowax 400 which are commerciallyavailable from Dow Chemical Company, alkoxylated polyols, such as PolyolR3215 and Polyol R3165 which are commercially available from PerstorpHolding AB, ethoxylated pentaerythritols, such as Polyol 4290 and Polyol4360 which are commercially available from Perstorp Holding AB,ethoxylated Sorbitols, such as Renex S 30 and Ethox 3692 which arecommercially available from Croda, non-ionic emulsified polyols,non-ionic diols and multifunctional polyols based on polyesters,polyethers and polyacrylates. Specific examples include Kuraray C-510,Stepanpol PD-195, Chempol 211-2224, etcetera. Examples of non-ionicpolyurethane dispersions include Witcobond W-320, W-320, W-322, andBondthane UD-410. It will be understood that, unless otherwisespecified, the chemical compounds provided herein, or their precursors,are available from common commercial chemical vendors, such asSigma-Aldrich Chemical Co., of St. Louis, Mo.

As will be discussed in greater detail below, the cationic-stabilizeddispersion formulations of the present invention preferably includeseveral other chemical compounds including, but not limited to,solvents, co-solvents, surfactants, substrate wetting agents, rheologymodifiers, pH modifiers, matting agents, defoaming agents, lubricitymodifiers, taber additives, fillers, pigments, color additives, tintingagents—the just to name a few.

One preferred solvent for use in accordance with the present inventionincludes water that has preferably been distilled, deionized, and/orfiltered via reverse osmosis, as well as polar, non-polar, protic, andaprotic solvents. Additional examples of solvents and/or co-solventsinclude propylene glycol n-butyl ether, propylene glycol monoethylether, glygol ether EB, proglyme—just to name a few. Preferably, theconcentration of the solvent/co-solvent in a net or overall formulationranges from approximately 0 percent by weight to approximately 95percent by weight, and more preferably ranges from approximately 5percent by weight to approximately 85 percent by weight, and yet morepreferably ranges from approximately 10 percent by weight toapproximately 75 percent by weight—depending upon the type ofcationic-stabilized dispersion.

In certain embodiments of the present invention, an anionic surfactantmay be utilized. Suitable examples include taurates; isethionates; alkyland alkyl ether sulfates; succinamates; alkylaryl sulfonates; olefinsulfonates; alkoxy alkane sulfonates; sodium and potassium salts offatty acids derived from natural plant or animal sources orsynthetically prepared; sodium, potassium, ammonium, and alkylatedammonium salts of alkylated and acylated amino acids and peptides;alkylated sulfoacetates; alkylated sulfosuccinates; acylglyceridesulfonates, alkoxyether sulfonates; phosphoric acid esters;phospholipids; and combinations thereof. Specific anionic surfactantscontemplated for use include, but are by no means limited to, ammoniumcocoyl isethionate, sodium cocoyl isethionate, sodium lauroylisethionate, sodium stearoyl isethionate, sodium lauroyl sarcosinate,sodium cocoyl sarcosinate, sodium lauryl sarcosinate, disodium laurethsulfosuccinate, sodium lauryl sulfoacetate, sodium cocoyl glutamate,TEA-cocoyl glutamate, TEA cocoyl alaninate, sodium cocoyl taurate,potassium cetyl phosphate, and combinations thereof.

In certain embodiments of the present invention, one or more cationicsurfactants may be utilized. Suitable examples include alkylatedquaternary ammonium salts R₄NX; alkylated amino-amides(RCONH—(CH₂)_(n))NR₃X; alkylimidazolines; alkoxylated amines; andcombinations thereof. Specific examples of anionic surfactantscontemplated for use include, but are by no means limited to, cetylammonium chloride, cetyl ammonium bromide, lauryl ammonium chloride,lauryl ammonium bromide, stearyl ammonium chloride, stearyl ammoniumbromide, cetyl dimethyl ammonium chloride, cetyl dimethyl ammoniumbromide, lauryl dimethyl ammonium chloride, lauryl dimethyl ammoniumbromide, stearyl dimethyl ammonium chloride, stearyl dimethyl ammoniumbromide, cetyl trimethyl ammonium chloride, cetyl trimethyl ammoniumbromide, lauryl trimethyl ammonium chloride, lauryl trimethyl ammoniumbromide, stearyl trimethyl ammonium chloride, stearyl trimethyl ammoniumbromide, lauryl dimethyl ammonium chloride, stearyl dimethyl cetylditallow dimethyl ammonium chloride, dicetyl ammonium chloride, dilaurylammonium chloride, dilauryl ammonium bromide, distearyl ammoniumchloride, distearyl ammonium bromide, dicetyl methyl ammonium chloride,dicetyl methyl ammonium bromide, dilauryl methyl ammonium chloride,distearyl methyl ammonium chloride, distearyl methyl ammonium bromide,ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium sulfate,di(hydrogenated tallow) dimethyl ammonium chloride, di(hydrogenatedtallow) dimethyl ammonium acetate, ditallow dipropyl ammonium phosphate,ditallow dimethyl ammonium nitrate, di(coconutalkyl)dimethyl ammoniumchloride, di(coconutalkyl)dimethyl ammonium bromide, tallow ammoniumchloride, coconut ammonium chloride, stearamidopropyl PG-imoniumchloride phosphate, stearamidopropyl ethyldimonium ethosulfate,stearimidopropyldimethyl (myristyl acetate) ammonium chloride,stearamidopropyl dimethyl cetearyl ammonium tosylate, stearamidopropyldimethyl ammonium chloride, stearamidopropyl dimethyl ammonium lactate,ditallowyl oxyethyl dimethyl ammonium chloride, behenamidopropyl PGdimonium chloride, dilauryl dimethyl ammonium chloride, distearlydimethyl ammonium chloride, dimyristyl dimethyl ammonium chloride,dipalmityl dimethyl ammonium chloride, distearyl dimethyl ammoniumchloride, stearamidoproyl PG-dimonium chloride phosphate,stearamidopropyl ethyldiammonium ethosulfate, stearamidopropyl dimethyl(myristyl acetate) ammonium chloride, stearimidopropyl diemthyl cetarylammonium tosylate, stearamido propyl dimethyl ammonium chloride,stearamidopropyl dimethyl ammonium lactate, and combinations thereof.

Likewise, any one of a number of commercially available, well-knownnon-ionic surfactants are contemplated for use, including, but notlimited to, alcohols, alkanolamides, amine oxides, esters (includingglycerides, ethoxylated glycerides, polyglyceryl esters, sorbitanesters, carbohydrate esters, ethoxylated carboxylic acids, phosphoricacid triesters), ethers (including ethoxylated alcohols, alkylglucosides, ethoxylated polypropylene oxide ethers, alkylatedpolyethylene oxides, and alkylated polypropylene oxides, alkylatedPEG/PPO copolymers). Specific examples of non-ionic surfactantscontemplated for use include, but are by no means limited to, cetearylalcohol, ceteareth-20, nonoxynol-9, C12-15 pareth-9, POE(4) laurylether, cocamide DEA, glycol distearate, glyceryl stearate, PEG-100stearate, sorbitan stearate, PEG-8 laurate, polyglyceryl-10 trilaurate,lauryl glucoside, octylphenoxy-polyethoxyethanol, PEG-4 laurate,polyglyceryl diisostearate, polysorbate-60, PEG-200 isostearylpalmitate, polysorbate-80, and combinations thereof.

In addition, any one of a number of commercially available, well-knownamphoteric surfactants are contemplated for use, including, but notlimited to, betaines; sultaines; hydroxysultaines, amido betaines,amidosulfo betaines; and combinations thereof. Specific examples ofamphoteric surfactants contemplated for use include, but are by no meanslimited to, cocoamidopropyl sultaine, cocoamidopropyl hydroxyl sultaine,cocoamidopropylbetaine, coco dimethyl carboxymethyl betaine, lauryldimethyl carboxymethyl betaine, lauryl dimethyl al phacarboxyethylbetaine, cetyl dimethyl carboxymethyl betaine, cetyl dimethyl betaine,lauryl (2-bishydroxy) carboxymethyl betaine, stearylbis-(2-hydroxyethyl) carboxymethyl betaine, oelyl dimethylgamma-carboxypropyl betaine, lauryl bis-(2-hydroxypropyl)alphacarboxymethyl betaine, coco dimethyl sulfopropyl betaine, stearyldimethyl sulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, laurylbis(2-hydroxyethyl) sulfopropyl betaine, oleyl betaine, cocamidopropylbetaine, and combinations thereof.

In one or more preferred embodiments of the present invention, thefollowing surfactants were found to be particularly beneficial assubstrate wetting agents, namely: Masurf FS-2800 (Mason ChemicalCompany) Byk-328 (BYK-Chemie), Byk-333 (BYK-Chemie), Byk-346(BYK-Chemie), Byk-348 (BYK-Chemie), Surfactol 365, Surfynol 104E (AirProducts), Surfynol GA (Air Products), Wet KL 245 (Tego-DegussaGoldschmidt), Novel TDA 30, and EFKA-4580 (EFKA-Ciba SpecialtyChemicals). Preferably, the concentration of the surfactant/substratewetting agent in a net or overall formulation ranges from approximately0.1 percent by weight to approximately 20 percent by weight, and morepreferably ranges from approximately 0.1 percent by weight toapproximately 5 percent by weight, and yet more preferably ranges fromapproximately 0.2 percent by weight to approximately 2 percent byweight—depending upon the type of cationic-stabilized dispersion.

Rheology modifiers for use in accordance with the present inventionpreferably include, for example, Borchigel PW25 (Lanxess Corporation),Alcogum L 520 (AkzoNobel), Aerosil 200 (Degussa), Rheolate 255(Elementis Specialties), Borchigel PW25 (Lanxess Corporation) andSN-Thickener 612 NC (San Nopco Korea Ltd.). Preferably, theconcentration of the rheology modifier in a net or overall formulationranges from approximately 0.1 percent by weight to approximately 20percent by weight, and more preferably ranges from approximately 0.5percent by weight to approximately 10 percent by weight, and yet morepreferably ranges from approximately 0.5 percent by weight toapproximately 5 percent by weight—depending upon the type ofcationic-stabilized dispersion.

PH modifiers for use in accordance with the present invention preferablyinclude, for example, Formic Acid, as well as other strong and weakacids. Preferably, the concentration of the pH modifier in a net oroverall formulation ranges from approximately 0.1 percent by weight toapproximately 20 percent by weight, and more preferably ranges fromapproximately 0.5 percent by weight to approximately 10 percent byweight, and yet more preferably ranges from approximately 0.5 percent byweight to approximately 5 percent by weight—depending upon the type ofcationic-stabilized dispersion.

Matting agents for use in accordance with the present inventionpreferably include, for example, Acematt TS100 silica and Syloid 55.Preferably, the concentration of the matting agent in a net or overallformulation ranges from approximately 0.1 percent by weight toapproximately 20 percent by weight, and more preferably ranges fromapproximately 0.5 percent by weight to approximately 10 percent byweight, and yet more preferably ranges from approximately 0.5 percent byweight to approximately 5 percent by weight—depending upon the type ofcationic-stabilized dispersion.

Defoaming agents for use in accordance with the present inventionpreferably include, for example, Agitan 299 (Ultra Additives), Byk-024(BYK-Chemie) polysiloxane, Byk-025 (BYK-Chemie), and Surfynol 104 BK(Air Products). Preferably, the concentration of the defoaming agent ina net or overall formulation ranges from approximately 0.1 percent byweight to approximately 20 percent by weight, and more preferably rangesfrom approximately 0.5 percent by weight to approximately 10 percent byweight, and yet more preferably ranges from approximately 0.5 percent byweight to approximately 5 percent by weight—depending upon the type ofcationic-stabilized dispersion.

Lubricity modifiers/taber additives for use in accordance with thepresent invention preferably include, for example, include Fluoroslip511 (Shamrock Technologies, Inc.), Rosilk 2229, and Microspersion 190.Preferably, the concentration of the lubricity modifier/taber additivein a net or overall formulation ranges from approximately 0.1 percent byweight to approximately 20 percent by weight, and more preferably rangesfrom approximately 0.5 percent by weight to approximately 10 percent byweight, and yet more preferably ranges from approximately 0.5 percent byweight to approximately 5 percent by weight—depending upon the type ofcationic-stabilized dispersion.

Fillers for use in accordance with the present invention preferablyinclude, for example, Sachtleben Micro (Sachtleben Corporation), Huber70 C (Huber Engineered Materials), and Steabright (Luzenac America).Preferably, the concentration of the filler in a net or overallformulation ranges from approximately 0.1 percent by weight toapproximately 20 percent by weight, and more preferably ranges fromapproximately 0.5 percent by weight to approximately 10 percent byweight, and yet more preferably ranges from approximately 0.5 percent byweight to approximately 5 percent by weight—depending upon the type ofcationic-stabilized dispersion.

Other compounds suitable for use in accordance with the presentinvention preferably include, for example, Z-6040 (Dow Corning) which isepoxy silane that crosslinks with KX-99 at room temp.

In one embodiment of the present invention, the process for fabricatingthe in-mold coated article comprises first applying a mold release agentto at least a portion of a tool surface. It will be understood thatapplying the mold release agent to the tool is optional. It will befurther understood that any one of a number of conventional mold releaseagents are suitable for use with the present invention. Next, one ormore of the cationic-stabilized dispersions disclosed herein isassociated with at least a portion of the tool surface and/or the moldrelease agent. Finally, a substrate is associated with the tool surfacehaving the optional mold release agent and the cationic-stabilizeddispersion to, in turn, generate an in-mold coated article.

The invention is further described by the following examples.

EXAMPLE 1

Material Amount (Wt. %) Hydran CP-7050  60-95% Lanco Liquimatt 6035 1-25% Surfynol 104BC 0.1-15% SN-Thickener 612 0.1-15%

EXAMPLE 2

Material Amount (Wt. %) PART A Ottopol KX-99  47-96% Syloid 75X55000.5-17% Michem Glide 37 0.5-15% Deionized Water  1-20% Byk 024  0.1-7%Surfynol 104BC 0.1-10% SN-Thickener 612 0.1-15% PART B Bayhydur LS2306 50-95% Butyl Acetate  10-50%Part A is mixed with Part B at a ratio of approximately 8:1.

PART C Material Amount (Wt. %) Dow Corning Z-6040 50-95% Butyl Acetate10-50%Part A is mixed with Part C at a ratio of approximately 6:1.

Additional formularies are provided in Examples 3-8 below.

EXAMPLE 3

Material Amount (Wt. %) Ottopol KX-99 50-95%  90% Formic Acid (aq.)0.1-5% Deionized Water  1-25% Byk 024 0.1-5% Fluoroslip 511 0.5-10% Acematt TS100 0.5-10%  Propylene Glycol n-butyl ether 0.5-10%  DeionizedWater  1-25% Byk 348 0.1-5% SN-Thickener 612 0.1-5%

Preferably the ratio (by weight) of the cationic-component to thesolvent/co-solvent ranges from approximately 12:1 to approximately 5:1,and preferably the ratio (by weight) of the cationic-component to thelubricity modifier/taber additive ranges from approximately 95:1 toapproximately 50:1.

EXAMPLE 4

Material Amount (Wt. %) Hydran CP-7050 50-98%  Byk 024 0.1-5% Syloid 55 1-25% Microspersion 190  1-25% Surfynol 104BC 0.1-5%

Preferably the ratio (by weight) of the cationic-component to thelubricity modifier/taber additive ranges from approximately 95:1 toapproximately 30:1.

EXAMPLE 5

Material Amount (Wt. %) Jeffamine T-5000  5-50% 90% Formic Acid (aq.)0.1-10%  Deionized Water 40-95% Fluoroslip 511  0.1-5%

Preferably the ratio (by weight) of the cationic-component to thesolvent/co-solvent ranges from approximately 0.2:1 to approximately1.5:1, and preferably the ratio (by weight) of the cationic-component tothe lubricity modifier/taber additive ranges from approximately 30:1 toapproximately 5:1.

EXAMPLE 6

Material Amount (Wt. %) Priamine 1074  5-50% 90% Formic Acid (aq.)0.1-10%  Deionized Water 40-95% Byk 024  0.1-5%

EXAMPLE 7

Material Amount (Wt. %) Hypro 2000X173 ATB 5-45% Propylene Glycolmonomethyl ether 1-10% Glycol Ether EB 2-20% Surfactol 365 0.1-5% Alcogum L-520 0.1-5%  90% Formic Acid (aq.) 0.1-10%  Deionized Water35-75% 

EXAMPLE 8

Material Amount (Wt. %) 90% Formic Acid (aq.) 0.1-10%  Deionized Water40-80%  Baxxodur EC 311  2-23% Triethylenetetramine (TETA) 0.1-5%Kuraray P-1010  1-15% Novel TDA 30 0.1-5% Ottopol KX-99  2-27% AdipicDihydrazide 0.1-5% Byk 024 0.1-5% Fluoroslip 511 0.5-10%  Byk 348 0.1-5%Reaxis C319 0.1-5% Proglyme 0.1-5% Rosilk 2229 0.1-5%

While the invention has been described in detail herein in accordancewith certain preferred embodiments thereof, many modifications andchanges therein may be effected by those skilled in the art.Accordingly, it is our intent to be limited only by the scope of theappending claims and not by way of details and instrumentalitiesdescribing the embodiments shown herein.

What is claimed and desired to be secured by the Letters Patent of theUnited States is:
 1. A cationic-stabilized dispersion formulation foruse in fabricating an in-mold coated article, comprising: a primarysolvent, wherein the primary solvent is present in a concentrationranging from approximately 2 percent by weight to approximately 50percent by weight; a secondary solvent, wherein the secondary solvent ispresent in a concentration ranging from approximately 0.5 percent byweight to approximately 10 percent by weight; a pH modifier, wherein thepH modifier is present in a concentration ranging from approximately 0.1percent by weight to approximately 5 percent by weight; a defoamingagent, wherein the defoaming agent is present in a concentration rangingfrom approximately 0.1 percent by weight to approximately 5 percent byweight; a taber additive, wherein the taber additive is present in aconcentration ranging from approximately 0.5 percent by weight toapproximately 10 percent by weight; a substrate wetting agent, whereinthe substrate wetting agent is present in a concentration ranging fromapproximately 0.1 percent by weight to approximately 5 percent byweight; a rheology modifier, wherein the rheology modifier is present ina concentration ranging from approximately 0.1 percent by weight toapproximately 5 percent by weight; a matting agent, wherein the mattingagent is present in a concentration ranging from approximately 0.1percent by weight to approximately 10 percent by weight; and a cationicchitosan polymer, wherein the cationic chitosan polymer is present in aconcentration ranging from approximately 0.1 percent by weight toapproximately 10 percent by weight.
 2. The cationic-stabilizeddispersion formulation according to claim 1, wherein the primary solventcomprises a polar solvent.
 3. The cationic-stabilized dispersionformulation according to claim 1, wherein the primary solvent compriseswater.
 4. The cationic-stabilized dispersion formulation according toclaim 1, wherein the secondary solvent comprises an alkyl ether ofpropylene glycol.
 5. The cationic-stabilized dispersion formulationaccording to claim 1, wherein the secondary solvent comprises propyleneglycol n-butyl ether.
 6. The cationic-stabilized dispersion formulationaccording to claim 1, wherein the pH modifier comprises an acid.
 7. Thecationic-stabilized dispersion formulation according to claim 1, whereinthe pH modifier comprises formic acid.
 8. The cationic-stabilizeddispersion formulation according to claim 1, wherein the taber additivecomprises a mixture of high melting synthetic wax andpolytetrafluoroethylene.
 9. The cationic-stabilized dispersionformulation according to claim 1, wherein the substrate wetting agentcomprises a polyether-modified siloxane.
 10. The cationic-stabilizeddispersion formulation according to claim 1, wherein the rheologymodifier comprises a urethane modified polyether.
 11. Thecationic-stabilized dispersion formulation according to claim 1, whereinthe matting agent comprises silica.
 12. The cationic-stabilizeddispersion formulation according to claim 1, wherein thecationic-stabilized dispersion comprises a cationic-stabilized polymericacrylic dispersion having approximately 10 to approximately 60 percentsolids, a Tg of approximately 15 degrees centigrade to approximately 50degrees centigrade, and a viscosity ranging from approximately 200centipoise to approximately 800 centipoise at 25 degrees centigrade.